Rubber-Toughened Plastics - ACS Publications - American Chemical

2 Rubber-Toughened Styrene Polymers Downloaded by UNIV ILLINOIS URBANA on February 27, 2013 | http://pubs.acs.org Publication Date: May 5, 1989 | doi: 10.1021/ba-1989-0222.ch002

A Review Adolf Echte Kunststofflaboratorium, B A S F Aktiengesellschaft, D - 6 7 0 0 Ludwigshafen, Federal Republic of Germany

This chapter surveys the possible ways to influence the molecular and morphological structures of rubber-toughened styrene polymers in industrial production processes. Two important types of produc tion processes are used in industry. Thefirstis polymerization of styrene monomer or its mixture with other monomers in the presence of dissolved rubber. The second is a graft polymerization of the monomer(s) onto preformed rubber in emulsion. In both cases, the structure of the dispersed rubber phase depends to a great extent on the process conditions. Transparent and very tough styrene-butadiene copolymers produced by anionic polymerization have recently become of interest. The most important characteristics of these two-phase or multiphase products are the molecular weight of the matrix; phase-volume ratio; type of particle, particle size, and size distribution; interfacial bonding; and rubber cross-linking den sity. The proper combination of all these properties has resulted in numerous novelties in high-impact polystyrene and acrylonitrilebutadiene-styrene copolymers, and it will continue to do so in the future.

w

H E N T H E D E M A N D FOR STYRENE MONOMER,

acrylonitrile, and sty-

rene-butadiene rubber (SBR) declined drastically in the late 1940s, the rubber modification of polystyrene (PS) and styrene-acrylonitrile copolymers (SAN) became of industrial interest. Since then, the so-called high-impact polystyrene (HIPS) and the rubber-toughened S A N (acrylonitrilebutadiene-styrene, ABS) have gained a broad market. In 1985 the con sumption of HIPS passed 3 Χ 10 tons per year (t/a), and ABS reached 1.5 X 10 t/a. Applications for HIPS are mainly packaging (United States, 30%; 6

6

0065-2393/89/0222-0015$13.50/0 © 1989 American Chemical Society

In Rubber-Toughened Plastics; Riew, C.; Advances in Chemistry; American Chemical Society: Washington, DC, 1989.

Downloaded by UNIV ILLINOIS URBANA on February 27, 2013 | http://pubs.acs.org Publication Date: May 5, 1989 | doi: 10.1021/ba-1989-0222.ch002

16

R U B B E R - T O U G H E N E D PLASTICS

Western Europe, 34%), appliances (United States, 8%; Western Europe, 8%), housewares (United States, 5%; Western Europe, 8%), and toys (United States, 6%; Western Europe, 3%); there are also many minor applications. The percentages are related to total polystyrene consumption, including expendable polystyrene (EPS), because it is not possible to differentiate the grades properly (I). ABS has been used mainly in automobile manufacture (United States, 18%; Western Europe, 25%; Japan, 19%), appliances (United States, 17%; Western Europe, 19%; Japan, 29%), electronics (United States, 9%; Western Europe, 17%), and pipes and fittings (United States, 15%; Western Europe, 2%), with a great number of minor applications. Polystyrene and S A N are transparent and brittle thermoplastic materials. The addition of rubber increases impact strength considerably, as can be seen from the stress-strain curves determined by an instrumental impact pendulum (Figure 1). SBR was replaced long ago by polybutadiene as a toughening agent in HIPS and A B S . Polybutadiene has a much lower glass-transition temperature (-85 °C) than SBR (-50 °C) (Figure 2) and therefore gives a much better low-temperature impact strength. This strength is required mainly in re frigerators, and to a lesser extent in automotive and some other applications. HIPS and A B S are two-phase materials. Buchdahl and Nielsen (2) showed this by dynamic mechanical testing of P S - S B R mixtures in 1950. Two phases also emerge clearly from T E M images made from microtome cut films stained by osmium tetraoxide, according to Kato (3). Such pictures even proved the dispersed phase to be of a two-phase nature, especially for HIPS and ABS made in bulk (Figure 3). " B u l k " as used here means polymerization of styrene in the presence of dissolved rubber. It comprises the continuous mass process, as well as the discontin uous mass suspension process to be discussed later. The particles contain relatively large inclusions of matrix material. Because of their appearance

Figure 1. Impact resistance of styrene polymers. SB is styrene-butadiene HIPS.



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Rubber-Toughened Styrene Polymers

17

F. *m »

Emulsion A B S

Bulk A B S

Figure 3. Morphology ofARS polymerized in emulsion or in bulk. (Reproduced with permission from réf. 4. Copyright 1979 Verlag Chemie.) in the images, we term this type of particles "cell particles". The inclusions enlarge the share of the rubbery phase far beyond the calculated rubber content. Therefore, as well as for other reasons, HIPS is made only in bulk. A B S , however, is produced either in bulk or in emulsion. Most pro ducers prefer the emulsion process to the bulk, generally because the op-


18


timum rubber particle size is much smaller and can be adjusted more easily by emulsion polymerization. In two-phase polymer systems, the technical properties do not depend solely on the properties of the pure components. In a complex way, numerous parameters affect the technical properties of the final products (List 1).


These molecular and morphological parameters can be brought into a scheme that may help the practitioner to choose the kind of operation nec essary for running a process according to the specifications of the products (Chart 1). Technical properties can be influenced during production processes by various suitable measures to be discussed later. In the cases of HIPS and FINISHED ARTICLE

MATRIX

MOLECULAR WEIGHT

STIFFNESS

TYPE OF RUBBER

TOUGHNESS

PHASE VOLUME RATIO

FLOWABJLITY

PARTICLE SIZE

HEAT DISTORTION MOLECULAR WEIGHT DISTRIBUTION

STRESS CRACK RESISTANCE GLOSS

ADDITIVES

SOFT COMPONENT

0

PARTICLE SIZE DISTRIBUTION PARTICLE

STRUCTURE

DEGREE OF GRAFTING

TRANSPARENCY

CROSSLINKING DENSITY OF THE RUBBER PHASE

WEATHERING RESISTANCE

List 1. Molecular and morphological parameters that influence technical properties. Modulus

Phase Volume Ratio

\

solvent flow impact - heat Gloss strength distortion crazing properties and/or tempérât; resistance transpar.

/

—

Particle Size and-Distribution Degree of Crosslin king

y

Matrix Molecular Weight

—

Lubricant concentration

/ /

—

/

\

\

\ y

\

y

y

\

—

/

y

Chart 1. Functional trends to adjust technical properties of HIPS.


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19

A B S , a measure that will improve one property affects practically all the others. Therefore, product development for market demand is always a question of optimization. Optimization requires the ability to adjust the different parameters separately, as far as possible without consequences for other parameters.


Production of HIPS or ABS in Bulk In principle, the bulk process consists of polymerizing styrene (or styrene-acrylonitrile) in the presence of dissolved rubber. Polystyrene is formed in the homogeneous rubber solution. The system then separates into two phases after a few percent of conversion, because the two polymer solutions are incompatible (Figure 4). The monomer is distributed between the two solvents, rubber and poly styrene. Because the amount of polystyrene increases with conversion and the amount of rubber remains constant, the polystyrene phase increases in volume at the expense of the rubber phase. When the phase-volume ratio approaches unity, phase inversion begins, and the rubber phase is distrib uted within the surrounding polystyrene phase (6, 7). The viscosity of the system increases in the same way, and the rubber-phase droplets become fixed in size at roughly 30-35% conversion (8). Conversion is then carried to a high level, and the residual monomers and any solvent are removed. Phase inversion can be observed with a phase-contrast microscope (9) and by viscosity measurements (5, 10) (Figure 5). Phase inversion occurs in

PS

PB

Figure 4. Phase diagram for PS-PB-styrene monomer. Key: A , starting point; B phase-separation point; C, final composition; D , phase-inversion point; E, composition of the polystyrene phase at phase inversion; F, composition of the polybutadiene phase at phase inversion. (Reproduced with permission from refi 5. Copyright 1983 Hanser.) y



20


Figure 5. Prepolymerization process. Polymerization of styrene in the presence of 6.4% dissolved polybutadiene rubber. Samples were taken at solids contents indicated. a rather broad conversion range. Under the microscope, it can be seen that the rubber phase itself is not homogeneous. Phase inversion occurs between a polystyrene solution and a subemulsion of polystyrene droplets in rubber solution. This subemulsion is the origin of the heterogeneous structure of the final rubber particles. Viscosity passes through a maximum-minimum with increasing conversion and shows a relatively broad transition span (Fig ure 6). This curvature may be quantitatively approximated by an equation put forward by Freeguard and Karmarkar (11) for the viscosity of a two-phase oil-in-oil emulsion. TU -

0.505 r j

c

(4> + φΡ + φί ) 1/3

c

(D

where η is viscosity, φ is volume fraction, Ε is emulsion, c is continuous phase, and d is dispersed phase. A more recent version was formulated by Song Zhiqiang and co-workers (12). This equation in the original paper was misprinted. It should read as indicated here. 1

A (I -

φ ) Ρ5

Β φ;T S


(2)


2.

ECHTE


0 I Ο

:

I 5

.

I 10

CONVERSION, %

21

•

L 15

Figure 6. Viscosity-conversion plot. (Reproduced with permission from ref 10. Copyright 1969 Wiley.) where R is rubber, PS is polystyrene, and A and Β are constants. Equations 1 and 2 are both derived from the power law for pseudoplastic liquids. In this reaction pathway, the molecular and morphological parameters of the final products must be adjusted to achieve the set of technical properties desired.

Molecular Weight of the Matrix Matrix molecular weight, which affects mainly mechanics and melt flow, is usually regulated by process conditions (temperature, initiator concentra tion, and solvent content) and by the addition of a suitable chain-transfer agent. fert-Dodecylmercaptan is commonly used for this purpose. Its transfer constant is roughly 4, and it is, therefore, effective for the whole course of the reaction. Mercaptans with primarily bound thiol groups are even more effective (transfer constant >20), but they exhaust at an early stage of conversion.


22



Otherwise, chain-transfer agents with transfer constants of about 0.1 (e.g., dimeric α-methylstyrene or terpinolene) become effective only when an advanced stage of conversion is reached. An increasing molecular weight means a higher melt viscosity. The higher the melt viscosity, the higher the molecular orientation in injectionmolded parts. Orientation imposes anisotropic behavior (Figure 7) that may be of greater influence on the properties than the molecular and morpho logical parameters in the isotropic state.

Type of Rubber In most cases the rubber type is polybutadiene. Its glass-transition temper ature depends on the microstructure (Table I). In practice it is -85 °C, sufficient for good low-temperature impact behavior. Because of its lack of

Figure 7. Influence of orientation on mechanical properties.


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23

Table I. Microstructure and Glass-Transition Temperature of Polybutadiene _CH

/CH -CH

2

2

/

c=c H

X

N

H

H'

c=c X

H

H

CH -CH 2

/CH = CH

N

c 2

C H

2

2

^

Components :%) ( Structure

1,4-cis

1,4-trans

1,2-Vinyl

T (°C)

98 35 24

1 55 54

1 10 22

-105 -85 -75


Ηϊφ-cis Medium-cis Emulsion

g

crystallinity, medium-ds-polybutadiene has slight advantages over high-cispolybutadiene. The melting point of high-ds-polybutadiene is roughly - 4 0 °C, and this negatively affects the low-temperature impact behavior of the final HIPS. The solution viscosity of the rubber used is important for the adjustment of the particle size in the reaction course, as will be discussed later. It depends on the molecular weight and on the degree of branching. Most polybutadienes

used commercially have molecular weights of between

180,000 and 260,000 (viscosity

average).

They are usually long-chain-

branched to suppress cold flow. Other rubbers occasionally used are S B R and E P D M (ethylene-propylene-diene-monomer

rubber), the latter yield

ing products with improved weatherability (13).

Phase-Volume Ratio Phase-volume ratio is influenced by the rubber content, by the number and size of occlusions, and by the degree of grafting. The early work of Cigna (14) indicates that the phase-volume ratio, as well as the rubber content, is decisive for the properties of a rubber-toughened styrene polymer. This finding was later confirmed by Bucknall et al. in a series of papers (15). Grafting at an early stage of polymerization turns the rubber solution in styrene into an emulsion of polystyrene solution in styrene dispersed in the rubber solution. This emulsion is stable enough that the polystyrene solution droplets will coalesce only partially, and the phase inversion takes place between a polystyrene solution and the unchanged emulsion. Thus, the dispersed rubber phase still contains inclusions of polystyrene solution. This step is how the inhomogeneity of the final rubber particles begins (7). The more polystyrene solution is trapped inside the polybutadiene (PB) phase after the phase inversion, the higher is the phase-volume ratio, P B / PS. Therefore the phase-volume ratio increases when grafting increases in the very early stages of the reaction, provided that the particle size is kept constant. The number and size of the occlusions depend on the reaction conditions.


24



If the reaction is carried out continuously in tower reactors or in a reactor cascade, as is usually the case, then the reaction pathway is not basically different from a discontinuous run, and the particles contain a large number of big inclusions in both cases (Figure 8A). If, however, the reaction is run in a continuous stirred tank reactor (CSTR) at elevated conversions, a relatively diluted rubber solution (6-10% solids) enters a reaction mass of some 60% solids, with polystyrene solution as the continuous phase. The entering feed solution is dispersed immediately in the reaction mass, losing monomer rapidly to it. This loss results in little grafting and only a few small inclusions within the particles, depending additionally on the residence time of the individual particles in the segre gated reactor. Consequently, the rubber efficiency (i.e., the ratio of the whole particle mass to its polybutadiene content) becomes poor (Figure 8B). Therefore, continuous industrial processes are run in reactor cascades or tower reactors.

Rubber-Particle Size The rubber-particle size spectrum comes into existence within the small conversion range between phase inversion and the high-viscosity stage. In this range, it is governed by three main influences: shear stress brought about by the agitator speed, the viscosity ratio of the two phases, and the interfacial tension between them. This dependence can be seen, at least qualitatively, from Flumerfelt's equation (16), which was derived from d i -

Figure 8. Rubber efficiency of cell particles. Particles were obtained by polymerizing a solution of polybutadiene in styrene: A, in a CSTR at 60% conversion; B, ina series of tower reactors, with sample taken at 60% conversion. Both samples were dried in vacuo at 213 °C and 1 mbar, cut, stained with OsQ , and tested by transmission electron microscopy (TEM). 4


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Rubber-Toughened Styrène Polymers

25

mensional analysis of viscoelastic fluids under shear stress and experimentally confirmed by means of several two-phase systems.


(3)

where D is the critical drop breakup diameter; K, K\ and β are constants; X is the time constant; σ is interfacial tension; r\ is the viscosity of the dispersed phase; η is the viscosity of the continuous phase; and τ is shear stress. The influence of agitator speed on particle size, crucial for the break through of the process in the early 1950s (17), has been shown in various publications (9,18,19). Particle size decreases with increasing agitator speed (Figure 9). At high shear the particle size levels out, and in the case of bulk ABS, Ide and Sasaki (19) observed reagglomeration at very high shear. c

d

0

The influence of the viscosity ratio with respect to drop breakup in a system of two immiscible fluids was studied by Rumscheidt and Mason (20) and Karam and Bellinger (21) in the 1960s (Figure 10). Rumscheidt and Mason demonstrated the mechanism of drop breakup at different levels of viscosity ratio, and Karam and Bellinger showed that the critical deformation D required for a drop to split off is at a minimum when the viscosity ratio approaches unity. This situation holds good qualitatively for polymerizing styrene-rubber solutions, but the quantitative correlations are much more complex because of the viscoelasticity of the two phases, discontinuity of shear, mass-transport phenomena, and other influences. In practice, in the phase-inversion regime the viscosity of the polybutadiene phase exceeds that of the polystyrene phase by a factor of 20 or more at 25 °C (5). This ratio, however, comes back to lower values because the rubber phase is itself an oil-in-oil emulsion. The influence of the viscosity ratio can be demonstrated by changing the phase viscosities separately. This step can easily be done by using rubbers of different molecular weights at a constant polystyrene molecular weight or by changing the polystyrene molecular weight at a constant polybutadiene molecular weight (9) (Figure 11). The third parameter for adjusting particle size is interfacial tension. It can be varied by suitable surfactants in this oil-in-oil emulsion, as has been shown by Molau (β). Graft copolymers and block copolymers of styrene and butadiene act as such surfactants; an increase in grafting or the addition of block copolymers in the early stages of polymerization reduces the particle size (Figure 12).



26


© m ο

Λ

··* . ·

.·

• © ®m®

® ·

9

~

1

' %" ' V

····

V βΓ··®.· β· · -'àiT · β

Α

θ.

*Γ

©Γ

Λ · · ®

"•V* ··.···.* J

.·•·.·

β · •

··"

®

β

?

·

β® ·

ό _ 1· 0.0 R P M ·.·• D = 0 . 6 6 μΓη

· ·

·

« ι

150 R P M D = 0 . 4 5 μητι

Figure 9. Particle size and agitator speed. D is mean particle diameter.

Grafting is generally considered to consist of primary radical attack on the rubber backbone. Most authors describe this reaction as hydrogen ab straction from the allylic position in the polybutadiene molecule (22-24), but recently arguments were put forward that grafting might be copolymerization (25). Nevertheless, grafting-active initiators like benzoyl peroxide greatly promote the reaction, whereas 2,2'-azobisisobutyronitrile (AIBN) does not (23). Rosen (26) has calculated the maximum possible degree of grafting / as a function of the conversion χ (Figure 13). This calculation assumes that grafting occurs only in the rubber solution and that every m a x


2.


ECHTE

INCREASING VISCOSITY


A

RATIO

1

2

3

1

2

3

1

1

27

2

Z

4

2

~

CR

16^+16%

5

4

3

U

5

4

3

4

0.001

0.01

INCREASING SHEAR RATE

VISCOSITY RATIO

(RUMSCHEIDT,

(KARAM, BELLINGER)

MASON)

η*/^

Figure 10. Drop breakup in a simple shearfield.The deformation Ό of a drop is given by the ratio (L-B)/(L + B), L being the major axis and Β the minor axis of the ellipsoidally deformed droplet in the shearfield.Key: γ is shear rate; η is viscosity; δ is Sauter diameter of the original drop; and σ is interfacial tension. Subscripts d and c mean discontinuous and continuous, respectively. (A: Reproduced with permission from refi 20. Copyright 1961 Academic. B: Reproduced from refi 21. Copyright 1968 American Chemical Society.)

INCREASING VISCOSITY RATIO

Figure 11. Particle size and viscosity ratio. D is mean particle diameter.


28


INFLUENCE OF ADDED S-B BLOCKCOPOLYMER ON PARTICLE SIZE


1 μηι

PB: 8% BCP: 0%

PB: 7,6 % BCP: 0,57%

PB: 7,2 % BCP: 1,14%

PB: 5,6 % BCP: 3,43%

Figure 12. Particle size and interfacial tension. Interfacial tension is supposed to drop by increasing block copolymer content.

0 . 10

0.08

Grafting Degree f

f max

•

peroxide initiation

• thermajjnitiation

I

0.06

0.0^

0.02

0.00 0.2

0.4

0.6

0.8

Conversion χ Figure 13. Maximum degree of grafting versus conversion. V is the volume of rubber solution and V is the volume of monomer at χ = 0. Experimental work was run discontinuously with 8% polybutadiene in styrene at 115 °C (thermal polymerization) and 80 °C (peroxide initiation). r

) n o

growing chain in this phase results in grafting. This upper limit is far from being attained, as the comparison with the experiment shows. In bulk A B S , furthermore, grafting is affected by preferential solubility of styrene in the rubber phase and of acrylonitrile in the matrix phase (27, 28). This preferential solubility cuts down the degree of grafting and affects a shift in composition between the grafts and the matrix copolymer.


2.

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29

Molau (29) has further shown that the block length of these surfactants must surpass a minimum value in the order of magnitude of the critical entanglement chain length to be able to make the two phases compatible.


Structure of Particles Block copolymers, furthermore, open up the possibility of change in the internal structure of the particles. Polymerization of styrene in the presence of preformed styrene-butadiene di-, tri-, or multiblock copolymers produces a multitude of different particle structures (9, 30-32) (Figure 14). These different structures are related to the morphological setup of the block copolymer used. Block copolymers exhibit crystallike domain arrays whose structure depends on their composition (Figure 15). Following M o lau's scheme (33), the domain structure of A - B block copolymers shifts with increasing Β content from spheres of Β in Α-matrix via cylinders of Β in A matrix to alternating lamellae of A and Β followed by the inverse structures. If styrene is polymerized in the presence of dissolved block copolymers, their domains are preserved in solution in the form of micelles when the concentration exceeds a critical value of about 9% (comparable to the con centration where the individual molecular coils in the solution come into contact). These micelles somehow retain the structure of the parent block copolymer. Additional grafting onto the polybutadiene part of the block

Shells

Rod Clusters

Droplet Clusters

Figure 14. Particle structures observed in HIPS. (Reproduced with permission from refi 32. Copyright 1982 Hanser.)



30


Figure 15. Block copolymer structures, schematic and observed. (Reproduced with permission from ref. 4. Copyright 1979 Verlag Chemie.)

copolymers leads to a higher polystyrene content in the ordered micelles. If this polystyrene content exceeds a certain critical limit, the structure of the micelles changes according to the corresponding structural change in the parent block copolymer, as if it had had a higher polystyrene content from the beginning. If this change happens before phase inversion, the type of particles generated afterward corresponds to the new micelle structure, or, in other words, to the block copolymer structure that belongs to this higher polystyrene content (Figure 16). This scheme could be sustained by comparing polymerizations with simulations where grafting had been totally excluded (9). The reaction pathway can be monitored by viscosity-conversion meas urements, as has been shown for polybutadiene. Structural change within the continuous rubber phase, as well as phase inversion, both manifest themselves in the sigmoidal shape of the viscosity-conversion curve (Figure 17). In the case of block copolymers, structural changes in the rubber phase are superimposed on the shape of the viscosity-conversion plot. The cor responding changes in structure can be made visible by electron micrographs taken of cast films. If styrene-butadiene-styrene (SBS) triblock copolymers are used in stead of the diblocks, the process runs basically the same way (Figure 18). There is one difference from the proceedings with SB diblocks: when these SBS triblocks contain much polybutadiene, very large particles that can hardly be split by the agitator are formed. Finally, in the case of butadiene-styrene-butadiene (BSB) triblock copolymers, onionlike shell particles or rod clusters or droplet clusters are obtained (Figure 19). These forms probably result from the ability of tri block copolymers to bridge the gap between two similar adjacent domains.



2.

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31


Figure 16. Particle structures from SB diblock copolymers. Particle structure related to domain structure: solid lines, without grafting; dotted lines, with grafting before phase inversion. (Reproduced with permission from ref. 4. Copyright 1979 Verlag Chemie.)

• conversion (%) Figure 17. Formation of capsule particles. Initial block copolymer concentration, 12%; temperature, 123 °C, 0.05% tert-dodecylmercaptan; viscosity taken from the torque of the agitator calibrated with liquids of known viscosity. (Reproduced with permission from ref 34. Copyright 1981 Verlag Chemie.) Bridging prevents these domains from separating during phase inversion (Figure 20). These findings were investigated further by simulated polymerizations (i.e., solution blendings) where no grafting reaction was possible (30). As a result, it can be established that if grafting doesn't interfere, the type of



32


Figure 18. Particle structures from SBS triblock copolymers. Particle formation during polymerization of styrene solutions.

Figure 19. Particle structure from BSB triblock copolymers. particles obtained corresponds to that of the basic block copolymer. Grafting shifts its primary composition to higher styrene content (Figure 21), and this shift brings about a change in the type of rubber particles. This concept holds good if the change in structure occurs before particle formation; in other words, before phase inversion (Figure 22). After this stage, in general, the particle morphology is stable against further grafting


2.

ECHTE

SPHERES AND RODS OF PS IN PB


SB

33


ALTERNATING LAMELLAS

0^0

SPHERES AND RODS OF PB IN PS

Θ--Θ

SEPARATION OF PB EASY



SEPARATION OF PB DIFFICULT






SBS

Β SB

Figure 20. Particle formation. The bridging ability of triblocks across the phases renders the separation of domains difficult when the phase to disperse or to dilute is bridged by the middle block of the triblock. (Reproduced with permission from ref. 30. Copyright 1980 Huthig and Wepf.)

Figure 21. Particle formation by graft polymerization or by solution blending. (Reproduced with permission from ref. 30. Copyright 1980 Hûthig and Wepf)


34



— P h a s e inversion

Figure 22. Block copolymer and rubber particles. and subsequent structural change because of the increasing viscosity of the system (Figure 23). If, however, phase inversion takes place just before the block copolymer micelles change their structure according to their altered composition, this change may still take place after phase inversion inside the just-formed particle, provided the viscosity is low enough. The result is disintegration of the primary cell particle to open labyrinths, capsules, or even rod clusters.

Rubber Cross-Link Density Rubber cross-link density is a further important factor. Rubber particles have to withstand the forces imposed by the different shrinkage of rubber and matrix when the melt cools to ambient temperatures. This situation builds up a triaxial stress field around the particles that is said to participate in craze nucleation under load. To prevent voiding inside the particles during solidification of the matrix, the rubber has to be cross-linked. To retain its elasticity and not to impair its glass-transition temperature and loss modulus, cross-linking must not be too intensive. The dependence of the swelling index of polybutadiene as a measure of its cross-link density on thermal treatment was elaborated by McCreedy and Keskkula (35) (Figure 24). Rubber particles in HIPS or ABS from the bulk processes are hetero geneous. Therefore, swelling in good solvents for both components is only a rough measure of the degree of cross-linking. Nevertheless, this method has been used up to now for practical reasons. Recently, Karam and Tien (36) put forward a quantitative analysis of the swelling behavior of a heter ogeneous gel on the basis of the modified Flory-Rehner equation. They succeeded in describing the cross-link density in these gels quantitatively when the proportion of occlusions is known. Because cross-linking is thermally activated, most cross-links are made in the devolatilization step of the continuous processes. This step is timeand temperature-dependent, and the process conditions have to be adapted to the swelling index desired.



2.


ECHTE

Figure 23. Structural changes inside preformed particles when the critical grafting degree is obtained not before but after phase inversion and particle formation.

1

5

10

20

30

40

60

200

TIME (h) Figure 24. Swelling index of polybutadiene versus time and temperature. (Reproduced with permission from ref. 35. Copyright 1979 Butterworth.)


36



Additives Common additives in HIPS are lubricants and antioxidants. The lubricant of choice is mineral oil. Alternatives (such as butyl stéarate and phthalic esters) were not able to keep up with this inexpensive and effective lubricant. As an inert material, the mineral oil is added in most cases to the polymer ization feed. It is usually present in amounts of 2-3% by weight. In some specialties, the amount of mineral oil may be lower (for better heat distortion stability) or higher (for easy flow). It lowers the glass-transition temperature of polystyrene by 3 °C per weight percent. The viscosity of HIPS is exactly correlated to the logarithmic blending rule (37): In η = (1 -

c) In η

ρ

+ c In η

οί1

(4)

where η is viscosity, c is concentration of oil, and subscript ρ indicates polymers. With this equation we can easily calculate the relative influences of both components. Antioxidants are usually taken from the group of hindered phenols. Several types are in common use. They protect HIPS efficiently against oxidative degradation, but no stabilizer is able to make HIPS (as well as ABS) sufficiently stable for long-term outdoor applications (carbon black being the exception). Occasionally, further additives are used in the resins for special appli cations. The most important are colors and pigments. Others are U V sta bilizers, antistatic agents, external lubricants, and mold-release agents. They all affect the properties to a certain extent, and their influence has to be tested in each case.

Industrial Processes Two kinds of processes to produce HIPS are currently in industrial use, both invented and developed in the early 1950s. One of them is run discontinuously, the other continuously. Both must allow for the adjustment of all the product parameters: grafting mainly before phase inversion, particlesize adjustment just after phase inversion, matrix molecular weight over the whole range of conversion, and cross-linking in the final stage of the reaction. The discontinuous process was elaborated by Monsanto (38). The facility consists of a prepolymerization vessel where mass polymerization is run in the presence of a graft-active radical initiator (e.g., dibenzoyl peroxide, ref. 21), and a second vessel for the suspension polymerization step, followed by equipment for finishing (Figure 25). In the prepolymerization stage, grafting creates sufficient emulsifying material and provides occlusion precursors. After phase inversion, particle size and structure are fixed by the agitator speed, by the phase-viscosity


2.

ECHTE

37


2

Rubber Chopper

Rubber Dissolver

Surge

0*0

— Filter

Prepolymeriser Weighing _ _ _ Hopper IJ^J

Centrifuge

Suspension polymeriser


Dryer Solution storage

Styrene storage

oo

ΐ Suspension

Bead storage

Make up . To P e l l e t i z i n g Extruder

Figure 25. HIPS; Mass suspension process. (Reproduced from ref. 39. Copy right 1981 American Chemical Society.)

ratio given by the respective molecular weights and concentrations of the polymers involved, and by the graft copolymer concentration. When the particles have been fixed in size and structure, the highly viscous reaction mass is dispersed in water with suspending agents. Poly merization is carried through nearly to completion by means of an oil-soluble high-temperature initiator and by stepwise increased temperatures. The final conversion and temperature determine rubber cross-linking. The continuous process was elaborated by Dow in the early 1950s (40) and was surveyed by Platzer (41). In this process, polymerization is per formed in bulk in a series of tower reactors (Figure 26). In the first reactor, grafting and phase inversion are followed by particlesize adjustment. In the second and third tower reactors, polymerization is taken to 80-85% conversion, and the volatiles are degassed from the reaction mass after it is superheated by flashing into a vacuum chamber. The polymer melt is then forwarded to granulation. In this section (devolatilization and melt transport) the rubbery phase cross-links, and each producer has a pro prietary set of conditions to get optimum quality. In the polymerization step, there are a great variety of reactor lines, details of which have been published. Most of these reactors are variants of the original three-tower process, suitable for optimizing grafting and particlesize adjustment (32) (Figure 27). Thus producers are able to adapt their product mix to market require ments and to launch new products fox new applications. Commercial HIPS commodities have matrix molecular weights (M ) of between 170,000 and w


38


Recover styrene and ethylbenzene

I

Ethylbenzene 15-25%)

Styrene 1 monomer

Reactor

L=tU


Heating and cooling tubes

Oowtherm - * » |

m\

Figure 26. Continuous bulk polymerization of styrene in the presence of dis solved rubber in a series of towers. A mixture of diphenyl and diphenyl oxide is circulated through grids of pipes with slow agitation for temperature control. (Reproduced from ref 41. Copyright 1970 American Chemical Society.) 220,000 and a dispersity index MjM of from 2.5 to 3.0. The rubber used preferentially is medium-ds-polybutadiene. The phase-volume ratio, based on a 6-10% rubber content, is normally between 25 and 35%, taken as gel content. The mean particle size is normally set at 2.5 μπι in diameter to obtain the optimum impact strength (42-44). The particles are most fre quently of the cell type. The swelling index is normally between 9.0 and 12.0, corresponding to the molecular weight of polybutadiene segments between cross-links of 10,000-30,000 (36). A common additive is mineral oil in the concentration range of 2-3%, the residual monomer content being less than 500 ppm. n

This old rubber-modified polystyrene, however, is still a subject of nov elties. For instance, B A S F has launched several series of new products in the past 12 years. One of them includes products with improved Frigenresistance that contain very large particles in combination with a high phase-volume ratio and some other adapted properties (45). In Europe they have taken a considerable share of the market in refrigerators from A B S . Another series recently launched consists of products with excellent gloss combined with high toughness. These materials are based on very small capsule particles, with a mean diameter of about 0.3 μπι and a small amount of cell particles (46). Products with pure capsule particle morphology are translucent and have excellent gloss, but only medium impact strength. In addition, products with excellent Izod toughness and fair gloss, as well as those with fair Izod toughness and very good gloss, have been com mercialized with good success (Figure 28). A l l these glossy impact products are apt to make inroads on diverse ABS applications.


2.

ECHTE

39


feed

Shell

degassing


feed

Monsanto

degassing

degassing

Mitsui Toatsu

degassing feed

!

•

Dow

! 1

M^

ΖΖ

i

prepolymerization

c ο 0 3 r>0 CO 00 ΟΟ . ΟΟ ·>0

: 3 ο c «Λ ? ΟΟ Ο *»

/

DO ΟΟ Οο ΟΟ ΟΟ

ΟΟ ο ο ο ο ΟΟ DO _30 o c ΟΟ o c ΟΟ

main polymerization reaction

degassing

Figure 27. Reactor cascades for HIPS production. (Reproduced with permis sion from ref. 32. Copyright 1982 Hanser.)

ABS: Properties and Production ABS (rubber-toughened acrylonitrile-butadiene-styrene copolymer) is a very versatile thermoplastic material for a broad range of applications. It can be made by bulk polymerization, and both discontinuous mass suspension and continuous bulk processes are in use (Figure 29). But the most common


40


Morphology, Izod Impact Strength and Gloss

Particle Diameter [pm] Izod Impact Strength [J/m]


Gloss (Arbitrary Units) (ABS-80)

5.6

2.8

1.0

125

140

180

18

35

60

76

Figure 28. Structure and properties of commercial HIPS-types, including the recent developments.

Figure 29. Morphology of ABS polymerized in emulsion or bulk. (Reproduced with permission from ref. 47. Copyright 1981 Council of Scientific and Industrial Research.) ABS process is emulsion polymerization, at least for the rubbery phase. Emulsion polymerization provides products with much smaller particles than the continuous bulk process. The emulsion process is run discontinuously in several steps (32) (Figure 30). First, a polybutadiene latex is produced. Butadiene polymerizes rather slowly. Small particles are made to reduce the cycle period and, in addition, the reaction is not run to completion. Because these particles are not of the


2.

ECHTE


41


butadiene recovery steam

SAN reactor

SAN dispersion

dryer

Figure 30. Production of ABS in emulsion. optimum size, a subsequent agglomeration step is necessary. This step is possible by the addition of suitable lattices with hydrophilic groups (48) or by a gradual decrease of the p H value by means of acetic anhydride (49). A grafting step follows particle agglomeration to the required size. Without the addition of extra ernulsifier, but with additional initiator together with the matrix monomers, a seeded polymerization is started to cover the par ticles with a matrix polymer shell. The graft dispersion (Figure 31) is mixed


42



with a S A N dispersion in suitable amounts, and the latex mixture is then precipitated by electrolytes, washed, dried, and processed to granules. The properties of these materials depend on the same molecular and morphological parameters as HIPS properties. Matrix molecular weight, rubber type, phase-volume ratio, rubber-particle size, particle structure, cross-link density, and additive content govern the technical properties. But there are some very important differences. Styrene-acrylonitrile copolymer is a polar matrix and therefore much more cohesive than poly styrene. This cohesiveness is considered to be the reason for the higher toughness of A B S , as is evident from the fact that ABS deforms not only by crazing but also by shear yielding (50, 51), which is activated by smaller particles than are usually present in HIPS. Furthermore, the matrix properties are influenced by composition, as well as molecular weight. The composition of both matrix and graft shell should be matched so that they will remain compatible. Deviations in acrylonitrile content of more than 5% cause incompatibility in S A N (52).

Molecular and Morphological Parameters Matrix and Molecular Weight. Matrix composition and molecular weight are determined by feed composition and reaction conditions. Styrene

Figure 31. ABS graft dispersion.


2.

ECHTE

43


and acrylonitrile have an azeotropic composition at 25% (by weight) acrylonitrile because of their copolymerization parameters of r = 0.4 and r = 0.04, respectively, in bulk polymerization. In emulsion polymerization, how ever, the azeotropic composition is 28.5% (by weight) acrylonitrile (53). Because the emulsion polymerization of the matrix and that of the graft shell are run discontinuously, the composition of the polymer is confined to a relatively narrow range of 28.5 ± 5% to avoid a shift in the chemical com position. In addition to this condition, the relatively high solubility of acrylo nitrile in water and the low solubility of styrene may lead to a shift in composition of the two monomers at the reaction site. This shift is particularly likely in the grafting reaction, in which it is superimposed by the different solubility of the two monomers in the primary rubber particles (27).


1

2

Rubber Type. The rubber type used in ABS is polybutadiene in most cases. It is made by emulsion polymerization, usually at 60 °C with potassium persulfate as initiator and sodium stéarate, rosin acid salts, or alkyl sulfonates as emulsifiers. The microstructure of the polybutadiene depends somewhat on the reaction temperature, and the cross-link density depends on the final conversion. Both parameters influence the glass-transition temperature. Polybutadiene is susceptible to oxygen attack. In finished articles, this mainly affects the polybutadiene particles in the surface and causes cavitation that acts as notches and causes bleaching (Figure 32). According to Stabenow and Haaf (54), clusters are the preferred path of oxygen attack; the cavitation causes flaws in the surface and makes the material brittle. Cavitation is hampered by closed graft shells around every particle, which prevent clus tering. Aery late rubbers and E P D M are sometimes taken to replace polybu tadiene in order to obtain better weatherability (Figure 33). Aery late rubbers

Ozone-attack

on ABS with Particle

Clusters

(schematic)

Figure 32. Surface cavitation by oxygen attack. (Reproduced with permission from ref. 54. Copyright 1973 Huthig and Wepf)



44


Figure 33. Rubber type and weatherability. (Reproduced with permission from ref. 47. Copyright 1981 Council of Scientific and Industrial Research.) are made in emulsion polymerization similar to polybutadiene and subse quently treated analogously to get acrylonitrile-styrene-acrylic ester co polymer (ASA); E P D M is used only in a bulk precipitation process. This process provides products with irregularly shaped rubber particles, acrylonitrile-(ethylene-propylene-terpolymer)-styrene copolymer (AES) (Figure 34). Because the rubbery and rigid phases of emulsion-polymerized ABS are made in separate reactors, the phase-volume ratio is determined by the blend ratio of the two components. As in HIPS, the phase-volume ratio has the greatest influence on impact strength. In contrast to HIPS, the rubber particles contain only a few or are not filled with matrix material occlusions. The total amount of polybutadiene in ABS polymers is therefore three or four times as high as in corresponding HIPS types (55). Impact strength increases with increasing rubber content (Figure 35). But, as in the case of HIPS, interfacial bonding by grafts and particle size are most important. In a series with a constant particle size and a constant degree of grafting, impact strength increases with the phase-volume ratio (56, 57). Young's modulus and yield stress decrease with the rubber content. The decrease in yield stress fits the Ishai-Cohen model very well, as was shown by Pavan and co-workers (58) (Figure 36). R u b b e r P a r t i c l e Size. In emulsion polymerization the rubber par ticle size is determined by a suitable choice of emulsifier concentration and



2.

ECHTE


45

Figure 34. AES particle structure. ~

Ε ο

2.0

TEMPERATURE (°C) Figure 35. Impact strength of ABS versus temperature and rubber content. (Reproduced with permission from ref 56. Copynght 1977 Applied Science.) mode of operation (monomer-to-water ratio, temperature). In principle, big rubber particles are made by reduced emulsifier concentration, by monomer feed, or by seeded polymerization. In practice, however, it is preferable to produce small particles within reasonable cycle times. The final particle size is adjusted afterward by agglomeration techniques; this approach leads to a In Rubber-Toughened Plastics; Riew, C.; Advances in Chemistry; American Chemical Society: Washington, DC, 1989.

46



3

RUBBER CONTENT (%) 0

y

versus rubber content at Τ=23 °C

RUBBER CONTENT (%) Young modulus versus rubber eontent at T= 23 °C

Figure 36. Stiffness of ABS versus rubber content. (Reproduced with permis sion from ref 58. Copyright 1985 Plastics and Rubber Institute.)

bimodal particle-size distribution of unagglomerated and agglomerated par ticles {Figure 37). In A B S polymers, the optimum particle size is much smaller than in HIPS. Because of the polar character of the matrix, the material tends to deform by shear yielding at low deformation rates. At higher deformation rates, crazes are nucleated (50). Very small particles make the A B S resins stiff, glossy, and less tough; big particles impair stiffness and gloss, but improve toughness (Figure 38). The optimum mean particle size for a good combination of toughness, stiffness, and surface gloss is about 0.3-0.5 μιη (47). Measurements of specimens processed under identical conditions show that gloss can be related exponentially to particle size (59).

Structure of Particles. The particle structure of emulsion-polymer ized A B S is of the core-shell type (Figure 39). Particles of polybutadiene must be tied in the surrounding matrix by a graft shell to provide good coupling of the two phases. The more closely covered the particle, the better the coupling and the more uniform the distribution in the matrix. Because the grafting is nearly complete (scarcely any free S A N polymer present after the graft reaction), the proportion of grafted S A N in the interface depends on the total amount of glassy monomer added and on the distribution of the grafted polymer between internal and external grafts. The proportion of graft copolymer included rises with increasing particle size and decreases with its cross-link density (47). In Rubber-Toughened Plastics; Riew, C.; Advances in Chemistry; American Chemical Society: Washington, DC, 1989.


2.

EGHTE


47

Figure 37. Bimodal particle-size distribution in ABS by agglomeration.

Figure 38. Particle size and mechanical properties of ABS. (Reproduced with permission from ref 47. Copyright 1981 Council of Scientific and Industrial

American Chemical Society Library 1155 16th St., N.W. In Rubber-Toughened Plastics; Riew, C.;

Advances in Chemistry; American Washington, DC, 1989. Washington, D XChemical . 2003Society: S


48


Figure 39. Structure of grafted particles in ABS. (Reproduced with permission from ref 47. Copyright 1981 Council of Scientific and Industrial Research.) Emulsion-grafted small particles exhibit a closed shell of graft copolymer on their surface, and no inclusions are visible in the images either before or after the mixing process. Bigger particles with low cross-link density have hardly any detectable graft shell, and the mixture with matrix polymer shows that the particles contain many large inclusions. If the cross-link density is enhanced, the graft shell becomes more clearly marked, but a considerable part of matrix polymer is still located inside the particle. If the size and cross-link density are constant, the amount of grafts is of crucial importance for the mechanical properties (Figure 40). If the particles are not completely covered by the graft shell, they will tend to agglomerate to large and irregularly shaped clusters during the mixing process, and the impact strength of the final ABS will depend on the mixing conditions. If the primary particles are small (0.1 μιη in diameter), an increase in grafting will first reduce the cluster dimensions to the optimum value. Con sequently, impact strength increases. If grafting is increased further, par ticles will be prevented from clustering and impact strength will drop again. With larger particles, less than 50% grafting is sufficient to obtain very tough materials, and products with bimodal particle-size distribution are even more advantageous (57). In contrast to HIPS, the internal structure of ABS is of minor influence on the mechanical properties. Most ABS types have more or less solid particles with few and small inclusions, depending on particle size and cross-link density. In A S A , however, grafting occurs mainly in the interior, even in highly cross-linked particles. The acrylate rubber is more



2.

ECHTE


49

Figure 40. Influence of degree of grafting on ARS structure. (Reproduced with permission from ref. 47. Copyright 1981 Council of Scientific and Industrial Research.) hydrophilic than the grafted matrix copolymer and therefore tends more to keep in contact with the aqueous milieu.

Cross-Linking. The cross-link density of rubber depends mainly on the final conversion in the butadiene polymerization. Additionally, the graft reaction and thermal treatment during the compounding step will contribute to the cross-linking. Little has been published on quantitative correlations to technical properties (60, 61).

Additives. There are no peculiarities in additives for ABS beyond those with HIPS. As a lubricant, mineral oil is not suitable because of the differences in polarity and therefore in solubility. The most important lu bricants are esters of phthalic acid and adipic acid, fatty acid esters of glycerol, and, in some cases, waxes. External lubricants are calcium or zinc stéarate, amides of fatty acids, or polyethylene waxes. Stearylethanolamine acts as an antistatic agent. ABS contains phenolic antioxidants similar to those used in HIPS; in special cases it also contains UV-absorbers. Flame retardancy is provided by high-bromine aromatics such as octabromodiphenyl ether, octabromodiphenyl, or tetrabromophthalic acid, all in combination with antimony oxide as a synergist (62).


50


The proper choice of the additive system, which depends on the ap plication of the final article, has to allow for additive influences on the whole set of properties of the product in service.


Specialty Styrenic Materials Styrenic materials are very versatile. They are easy to process and they have a good overall price-performance relationship. But for a series of applica tions, they fail to meet the requirements. The most important properties involved are transparency (in combination with high impact strength) and heat distortion temperature. Transparency. The two-phase nature of impact-grade styrenic ma terials causes turbidity by light scattering at the dispersed phase. This effect occurs because the particles are often larger than the wavelength of light or their size lies in its order of magnitude, and because they exhibit refractive indices different from those of the matrix (Figure 41). According to M i e s theory, the turbidity coefficient depends on both particle diameter and re fractive index difference (63). If the diameter of the particles is small enough with respect to the wavelength of visible light (some 0.05 part of it), they can be considered

Ix/I

0

- exp [-(ε + τ ) χ ]

10

10

2

particle diameter/um

refractive index difference

Figure 41. Light scattering dependence on particle size and refractive index difference. Key: τ is the turbidity coefficient; e is the extinction coefficient; χ is sample thickness; and I and I are the intensity of the entering and leaving beam, respectively. (Reproduced with permission from ref. 4. Copyright 1979 Verlag Chemie.) D

x



2.

ECHTE


51

optically homogeneous in spite of their real domain structure, and their cumulative refractive index can be calculated by linear interpolation from the components. The refractive index of the composite particle is lower than that of the S A N matrix (—1.57) but higher than that of polybutadiene (1.52). Polymethyl methacrylate (PMMA) is compatible with S A N to a certain de gree, and its refractive index (1.49) is lower than that of the particle. It is, therefore, possible to match the refractive indices of the matrix and the grafted rubber by blending the matrix with some P M M A to get transparent materials. This approach holds good for monomodally distributed grafted particles. However, the degree of grafting of bimodally distributed particles depends on their specific surfaces, which is smaller with larger particles. Therefore, the refractive indices of small and big particles become different, and the products turn turbid even if the calculated composition of the grafted rubber matches the matrix refractive index (Figure 42). Clusters of particles act as scattering centers like single particles. Trans parency therefore also depends on the dispersion of the particles in the matrix (i.e., on the processing conditions). As a result, transparent items

Figure 42. Particle size distribution and transparency. (Reproduced with permission from ref 4. Copyright 1979 Verlag Chemie.)


52

R U B B E R - T O U G H E N E D PLASTCCS

may turn turbid on annealing if they first were in a nonequilibrium state of dispersion, and agglomerate later because of the lack of shearing forces when heated again above their glass-transition temperature. It is possible to calculate the diameter of a sphere optically equivalent to the cluster from a Guinier plot of the intensity of scattered light against the scattering angle (Figure 43).


Scattering intensity is also affected by the spatial arrangement of the scattering centers. Styrene-butadiene block copolymers are highly trans-

Figure 43. Clustering and transparency. (Reproduced with permission from ref 4. Copyright 1979 Verlag Chemie.)


2.

ECHTE


53


parent, although they are separated in domains of different refractive indices (Figure 44). These domains are not small enough to explain the excellent transparency. One can characterize the influence of regularity by a lattice factor L and consider the intensity of scattered light to be a product of the squares of this lattice factor and a particle factor Ρ (4, 47). In the region of visible light, the low lattice factor compensates for the higher particle factor to cause transparency. At very low wavelengths with small-angle X-ray scattering, a steep increase in the lattice factor with a maximum at 0.3° leads to the intensity distribution well known from the regular structure of block copolymers. Styrene-butadiene block copolymers are not compatible with polysty rene (64) if its molecular weight exceeds that of the polystyrene block in the copolymer. Therefore, 1:1 blends of block copolymers with polystyrene are more turbid than the parent materials (Figure 45). Extruder blends with a fine dispersion of the two components show only slight turbidity, which is greatly increased when the sample is annealed. This increase stems from the separation of the frozen-in nonequilibrium state of the extruder blend, as can be shown by electron microscopy. This result proves that the regular arrangement of the domains is decisive for the high transparency of block copolymers (47). Such block copolymers are very interesting products as transparent im pact-resistant polystyrenes (Figure 46). The structure is, of course, very different from that of a conventional rubber-modified product. Star-shaped styrene-butadiene block copolymers were developed to obtain a transparent, impact-resistant, and easily processable product. They have been available on the market since the early 1970s. Symmetrical and asymmetrical structures are described in the patent literature (65-68) (Figure 47). Star-block copolymers are made by several versions of multistep anionic copolymerization. The principal structure is starlike, with polybutadiene or polystyrene in the core and with polystyrene endblocks at all or only some of the polybutadiene branches. These products are highly transparent and very tough, and therefore are a very useful extension of the rubber-modified polystyrene family (Figure 48). Transparency can also be attained by matching refractive indices. C o n sequently, a blend of SAN-grafted rubber with a blend matrix of S A N and P M M A of appropriate composition yields transparent ABS types. However, P M M A and S A N are compatible only if the S A N contains 12-22% acrylonitrile (4). H e a t D i s t o r t i o n . Heat distortion is directly related to the glass-tran sition temperature of the polymer and to the content of additives. Styrenic materials have their glass transition at about 100 °C. Two methods can be used to extend their applicability: copolymerization and blending.




• ' • ' ι »—»—ι 500

200

1 100

1 1

1

1

ι — 1

50

1

1

Γ

20

10

X=îf

Hn(*/é)

Figure 44. Block copolymer transparency. (Reproduced with permission from ref. 4. Copyright 1979 Verlag Chemie.)



2.

ECHTE

55


Figure 45. Block copolymer-homopolymer mixtures. (Reproduced with permission from réf. 47. Copyright 1981 Council of Scientific and Industrial Research.)

Copolymerization is confined to only a few comonomers. a-Methylstyrene has found limited application in the A B S field as a partial substitute for styrene, bringing the glass transition up to 115 °C in practical cases. Recently, p-methylstyrene was claimed to be able to replace styrene mon omer to a considerable extent (69). Poly-p-methylstyrene has a glass-tran sition temperature (T ) of 108 °C, slightly above the temperature of boiling water. Furthermore, maleic anhydride (MA) is sometimes used as a suitable comonomer for styrene. Rubber-modified types with a glass-transition tem perature in the range of 110-150 °C are available according to the M A content. Roughly, the T is raised by 3 °C per weight percent of M A in the polymer (70). The impact strength of these polymers is comparable to that of medium-impact polystyrene. The manufacture of these polymers is com plicated by the disparity in copolymerization parameters (r = 0.01, r = ~0), which favors alternating copolymerization. g

g

1

2

The most versatile method of preparing styrenic materials with a high heat-distortion temperature is blending. Blending can be done with both compatible and incompatible components. Polystyrene is compatible on a molecular scale with poly-2,6-dimethylphenylene ether (PPE) (71) and also with tetramethylbisphenol-A-polycarbonate (72). The P P E blend has had a good market since the late 1960s, and it is still growing; the polycarbonate blend was of only temporary interest. H I P S - P P E blends have glass-transition temperatures of 100-200 °C (Figure



56


0,5 pm Figure 46. Morphology of conventional HIPS and transparent anionically polymerized grades.

49). In practice, this range is 110-140 °C, because the values are influenced not only by the blend ratio, but also by additives. These blends exhibit the same morphology as the parent HIPS (i.e., cell particles). Their optimum size is smaller than that found in conventional HIPS, as presented in 1977 by Cooper et al. (73). One of their major benefits is the possibility of providing halogen-free flame-retardant formulations (Fig ure 50).



ECHTE


BUTADIENE-CONNECTION

STYRENE-CONNECTION

Figure 47. Molecular structure patterns of star-block copolymers.

Figure 48. Transparent HIPS application.



58


*

Weight 7. PPO

Figure 49. Glass transition of PPE-PS blends.

•

high heat resistance

•

high impact strength

φ high dimensional stability •

high hydrolytic stability

•

halogen-free flame retardant agents

Figure 50. Features of HIPS-PPE blends.


2.

ECHTE

59


The second blend of commercial interest consists of A B S and polycar bonate (PC). S A N , the matrix material of the A B S , and P C are only semicompatible. These blends exhibit their two-phase nature in electron micrographs and in T as well (74) (Figure 51). g


A B S - P C contains, in addition to P C - S A N , a rubber as a third phase (Figure 52). The properties of these blends depend on their mixing conditions and morphology (Figure 53). If ABS is the continuous phase, the notched Izod impact strength is similar to that of the ABS component. If P C is the continuous phase, impact strength increases considerably. By contrast, ten sile strength increases linearly with an increasing P C content (75). Impact behavior also depends on dispersity and, therefore, on blending and processing conditions. The higher the processing temperature, the coarser the phase distribution (76). If ABS is the continuous phase, a brittleto-tough transition can be observed at low test temperatures but cannot be seen in the case of a continuous P C phase (76). Not only A B S but also A S A is a very useful blending component for P C . In addition to the advantages of A B S - P C , it provides a good outdoor per formance, light natural color, and good yellowing resistance (Figure 54). Blending is not confined to the examples mentioned (Figure 55). It has been extended to the whole range of thermoplastic materials, and much more work is going to be done in the field of multiphase polymer blends. Styrenic materials are full of interesting and challenging novelties in

Tg[°C]

0/100

PC/SAN 60:40

50/50

100/0

PC/SAN (MORBITZER ET AL.)

Figure 51. Phase structure (left) and glass transition of S AN-PC blends. (Reproduced with permission from ref. 74. Copyright 1985 Huthig and Wepf)



60


Figure 52. Morphological structure of ABS-PC blends.

YIELD STRENGTH (psi)

NOTCHED IZOD IMPACT (ft-lb/in. notch) 20

8000 H 15 H 7000 H 10^ 6000 H

POLYCARBONATE (%)

0

Γ 50 POLYCARBONATE(%)

100

Figure 53. Properties of ABS-PC blends versus composition. (Reproduced with permission from ref. 75. Copyright 1984 Wiley.)


ECHTE


• • • • • • •


high resistance to heat deformation good rigidity and dimensional stability great toughness good outdoor performance and resistance to yellowing comparatively good resistance to environmental stress crackin efficient antistatic no problems in processing

Figure 54. Features of ASA-PC blends.

Figure 55. Multiphase polymer blends; examples.


62

R U B B E B - T O U G H E N E D PLASTICS

research and development. Although they are more than 50 years of age, their possibilities are far from being exhausted. We have every reason to look forward to the next decade.


Acknowledgments This chapter is dedicated to Prof. D r . Helmut Dôrfel on the occasion of his 60th birthday. The author is indebted to G . Heckmann and J. Stabenow for providing the electron micrographs, to H . P. Hofmann and H . D . Schwaben for helpful discussions and kind support, and to Β. E . Byrt for reading the manuscript.

References 1. Anonymous Mod. Plast. Int. 1986, 16 (1), 24; Anonymous Mod. Plast. Int. 1987, 17 (1), 20. 2. Buchdahl, R.; Nielsen, L. E . J. Appl. Phys. 1950, 21, 482. 3. Kato, K. J. Electron Microsc. 1965, 14, 219; Polym. Eng. Sci. 1967, 7, 38. 4. Schmitt, B. J. Angew. Chem. 1979, 91, 286. 5. Riess, G . ; Gaillard, P. In Polymer Reaction Engineering; Reichert, Κ. H . ; Geiseler, W., Eds.; Hanser: Munich, 1983; p 221. 6. Molau, G. E . J. Polym. Sci. Part A-1 1965, 12, 67; ibid. 4235. 7. Molau, G. E.; Keskkula, H . J. Polym. Sci. Part A-1 1966, 4, 1595. 8. Bender, B. W. J. Appl. Polym. Sci. 1965, 9, 2887. 9. Echte, A. Angew. Makromol. Chem. 1977, 58/59, 175. 10. Molau, G. E.; Wittbrodt, W. M . ; Meyer, V. E . J. Appl. Polym. Sci. 1969, 13, 2735. 11. Freeguard, G. F.; Karmarkar, M . J . Appl. Polym. Sci. 1971, 15, 1649. 12. Zhiqiang, Song; Huigen, Yuan; Zuren, Pen J. Appl. Polym. Sci. 1986, 32, 3349. 13. Freund, G . ; Lederer, M . ; Strobel, W. Angew. Makromol. Chem. 1977, 58/59, 199. 14. Cigna, G. J. Appl. Polym. Sci. 1970, 14, 1781. 15. Bucknall, C. B.; Cote, F. F. P.; Partridge, I. K. J. Mater. Sci. 1986, 21, 301; Bucknall, C. B . Davies, P.; Partridge, I. K. J. Mater. Sci. 1986, 21, 307; Buck nall, C. B; Davies, P.; Partridge, I. K. J. Mater. Sci. 1987, 22, 1341. 16. Flumerfelt, R. W. Ind. Eng. Chem. Fundam. 1972, 11, 312. 17. Amos, J. L . Polym. Eng. Sci. 1974, 14, 1. 18. Freeguard, G. F. Br. Polym. J. 1974, 6, 205. 19. Ide, F.; Sasaki, I. Kobunshi Kagaku 1970, 27, 617. 20. Rumscheidt, F. D . ; Mason, S. G. J. Colloid Sci. 1961, 16, 238. 21. Karam, H . J . ; Bellinger, J. C. Ind. Eng. Chem. Fundam. 1968, 7, 576. 22. Fischer, J. P. Angew. Makromol. Chem. 1973, 33, 35. 23. Brydon, Α.; Burnett, G. M . ; Cameron, G. G. J. Polym. Sci. Polym. Chem. Ed. 1973, 11, 3255; ibid. 1974, 12, 1011. 24. Gupta, V. K.; Bhargava, G. S.; Bhattacharyya, Κ. K. J. Macromol. Sci. Chem. A 1981, 16, 1107. 25. Hayes, R. Α.; Futamura, S. J. Polym. Sci. Chem. Ed. 1981, 19, 985. 26. Rosen, S. L . J. Appl. Polym. Sci. 1973, 17, 1805. 27. Locatelli, J. L . ; Riess, G. Makromol. Chem. 1974, 175, 3523. 28. Locatelli, J. L . ; Riess, G. J. Polym. Sci. Polym. Chem. Ed. 1973, 11, 3309. ;


63

ECHTE

29. 30. 31. 32.

Molau, G. E . Kolloid Ζ. Z. Polym. 1970, 238, 4931. Echte, Α.; Gausepohl, H . ; Lütje, H . Angew. Makromol. Chem. 1980, 90, 95. Riess, G . ; Schlienger, M . ; Marti, S. J. Macromol. Sci. Phys. B 1980, 17, 355. Echte, A. In Chemische Technologie, 4th ed.; Harnisch, K.; Steiner, R.; Winnacker, K., Eds.; Hanser: Munich, 1982; Vol. 6, p 373. Molau, G. E . In Block Polymers; Aggrawal, S. L . , E d . ; Plenum: New York, 1970; p 79. Echte, Α.; Haaf, F.; Hambrecht, J. Angew. Chem. Int. Ed. Engl. 1981, 20, 344. McCreedy, K.; Keskkula, H . Polymer 1979, 20, 1155. Karam, H . J . ; Tien, L. J. Appl. Polym. Sci. 1985, 30, 1969. Kruse, R. L . ; Southern, J. H . Polym. Eng. Sci. 1979, 19, 815. Stein, R. S.; Walter, R. L. U.S. Patent 28 62 907, 1958, to Monsanto Chemical Company. Pohlemann, H . G . ; Echte, A. In Polymer Science Overview; Stahl, G. Α., E d . ; ACS Symposium Series 175; American Chemical Society: Washington, D C , 1981; p 265. Amos, J. L.; McCurdy, J. L.; McIntryre, O. R. U.S. Patent 26 94 692, 1954, to Dow Chemical Company. Platzer, N. Ind. Eng. Chem. 1970, 62 (1), 6. Donald, A. M . ; Kramer, E . J. J. Appl. Polym. Sci. 1982, 27, 3729. Bucknall, C. B.; Davies, P.; Partridge, I. K. J. Mater. Sci. 1987, 22, 1341. Gilbert, D. G.; Donald, A. M . J. Mater. Sci. 1986, 21, 1819. Mittnacht, H . ; Jenne, H . ; Bronstert, K.; Lieb, M . ; Adler, H. J.; Echte, A. U.S. Patent 41 44 204, 1979, to BASF AG. Echte, Α.; Gausepohl, H. U.S. Patent 44 93 922, 1985, to BASF AG. Haaf, F.; Breuer, H . ; Echte, Α.; Schmitt, B. J.; Stabenow, J. J. Sci. Ind. Res. 1981, 40, 659. Keppler, H . G . ; Wesslau, H . ; Stabenow, J. Angew. Makromol. Chem. 1968, 2, 1. Paster, M . D. U.S. Patent 39 88 010, 1976, to Monsanto Company; U.S. Patent 40 43 955, 1977, to Monsanto Company. Bucknall, C. B.; Drinkwater, I. C. J. Mater. Sci. 1973, 8, 1800. Bucknall, C. B. Adv. Polym. Sci. 1978, 27, 121. Molau, G. E . J. Polym. Sci. Polym. Lett. Ed. 1965, 3, 1007. Lin, Chen-Chong; Ku, Hwar-Ching; Chiu, Wen-Yen J. Appl. Polym. Sci. 1981, 26, 1327. Stabenow, J . ; Haaf, F. Angew. Makromol. Chem. 1973, 29/30, 1. Bucknall, C. B. Toughened Plastics; Applied Science: London, 1977; p 104. Bucknall, C. B. Toughened Plastics; Applied Science: London, 1977; p 298. Morbitzer, L . ; Kranz, D . ; Humme, G . ; Ott, K. H . J. Appl. Polym. Sci. 1976, 20, 2691. Riccò, T.; Rink, M . ; Caporusso, S.; Pavan, A. International Conference; Toughening of Plastics II; Plastics and Rubber Institute: London, 1985; Vol. 27, pp 2-3. Lednicky, F.; Pelzbauer, Ζ. Angew. Makromol. Chem. 1986, 141, 151. Bohn, L. In Copolymers, Polyblends, and Composites; Platzer, Ν. Α., E d . ; Advances in Chemistry 142; American Chemical Society: Washington, D C , 1975; p 66; Angew. Makromol. Chem. 1971, 20, 129. Morbitzer, L . ; Ott, Κ. H . ; Schuster, H . ; Kranz, D. Angew. Makromol. Chem. 1972, 27, 57. Brighton, C. Α.; Pritchard, G . ; Skinner, G. A. Styrene Polymers Technology and Environmental Aspects; Applied Science: London, 1979; p 236. Conaghan, B. F.; Rosen, S. L. Polym. Eng. Sci. 1972, 12, 134.

33.



2.

34. 35. 36. 37. 38. 39.

40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50. 51. 52. 53. 54. 55. 56. 57. 58.

59. 60.

61. 62. 63.


64

64. 65. 66. 67.


68. 69. 70. 71. 72. 73. 74. 75. 76.


Inoue, T.; Soen, T.; Hashimoto, T . ; Kawai, H . Macromolecules 1970, 3, 87. Zelinski, R. P.; Hsieh, H. L. U . S . Patent 32 81 383, 1966, to Phillips Petroleum Company. Kitchen, A . G.; Szalla, F. J. U . S . Patent 36 39 517, 1972, to Phillips Petroleum Company. Fahrbach, G.; Gerberding, K . ; Seiler, E . ; Stein, D . U . S . Patent 40 86 298, 1978, to B A S F A G . Fahrbach, G.; Gerberding, K . ; Seiler, E.; Stein, D . U . S . Patent 41 67 545, 1979, to B A S F A G . Keading, W . W.; Young, L . B . ; Prapas, A . G . CHEMTECH 1982, 12, 556. Dean, B. D . J. Elastomers Plast. 1985, 17, 55. Jelenic, J.; Kirste, R. G.; Oberthür, R. C.; Schmitt-Strecker, S.; Schmitt, B. J . Makromol. Chem. 1984, 185, 129. H u m m e , G.; Röhr, H.; Serini, V. Angew. Makromol. Chem. 1977, 58/59, 85. L e e , G . F . ; Katchman, Α . ; Shank, C . P.; Cooper, G . D . Polym. Prepr. (Am. Chem. Soc. Div. Polym. Chem.) 1977, 18 (1), 842. Morbitzer, L.; Kress, H . J.; Lindner, C.; Ott, Κ. H. Angew. Makromol. Chem. 1985, 132, 19. Suarez, H.; Barlow, J. W.; Paul, D . R. J. Appl. Polym. Sci. 1984, 29, 3253. Weber, G.; Schoeps, J. Angew. Makromol. Chem. 1985, 136, 45.

R E C E I V E D for review February 11, 1988. A C C E P T E D revised manuscript September 7, 1988.


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